Surface modification of nanocrystalline diamond/amorphous carbon composite films

The surfaces of nanocrystalline diamond/amorphous carbon (NCD/a-C) nanocomposite films deposited from a 17% CH₄/N₂ mixture have been subjected to a variety of plasma and chemical treatments, namely H₂ and O₂ microwave plasmas, a CHF₃ 13.56 MHz plasma, and a chemical treatment with aqua regia (HCl:HNO₃ 3:1). The resulting surfaces have been studied with respect to their chemical nature by X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectrometry (TOF-SIMS), concerning their morphology with atomic force microscopy, and by contact angle measurements to study their hydrophobicity and their stability. As-grown surfaces are hydrogen terminated, but the number of C–H bonds can slightly be increased by a H₂ microwave plasma, while treatment with aqua regia considerably lowers the number of C–H bonds at the surface. O₂ and CHF₃ plasmas, on the other hand, lead to a replacement of the terminating C–H bonds by C–O or C–OH and C–F_x groups, respectively. Finally, by contact angle measurements over a period of 150 days it could be shown that the H-terminated surface is very stable whereas the contact angle of the O-treated surface changed considerably with time, probably due to the adsorption of contaminants.     

Structural investigation of nanocrystalline diamond/amorphous carbon composite films

Nanocrystalline diamond/amorphous carbon (NCD/a-C) composite films have been prepared by microwave plasma chemical vapor deposition (MWCVD) from methane/nitrogen mixtures. The complex nature of the coatings required the application of a variety of complementary analytical techniques in order to elucidate their structure. The crystallinity of the samples was studied by selected-area electron diffraction (SAED). The diffraction patterns revealed the presence of diamond crystallites within the films. From the images taken by transmission electron microscopy (TEM) the crystallite size was determined to be on the order of 3–5 nm. The results were confirmed by X-ray diffraction (XRD) measurements exhibiting broad (111) and (220) peaks of diamond from which the average size of the crystallites was calculated. The grain boundary width is 1–1.5 nm as observed by TEM images which corresponds to a matrix volume fraction of about 40–50%. This correlates very well with the crystalline phase content of about 50% in the films estimated from their density (2.75 g/cm³ as determined by X-ray reflectivity). The bonding structure of the composite films was studied by electron energy loss spectroscopy (EELS) in the region of carbon core level. The spectra were dominated by a peak at 292 eV indicating the diamond nature of the investigated films. In addition, the spectra of NCD/a-C films possessed a shoulder at 284 eV due to the presence of a small sp² bonded fraction. This phase was identified also by X-ray photoelectron spectroscopy (XPS). The sp²/sp³ ratio was on the order of 10% as determined by deconvolution of the C1s XPS peak.     

Mechanical properties of nanocrystalline diamond/amorphous carbon composite films prepared by microwave plasma chemical vapour deposition

Nanocrystalline diamond films (NCD) have been deposited by microwave plasma chemical vapour deposition from CH₄/N₂ mixtures with varying methane content. They consist of diamond nanocrystallites with sizes of 3–5 nm embedded in an amorphous matrix with grain boundary widths of 1–1.5 nm. The CH₄ content in the gas phase has almost no influence on the microscopic structure but a strong effect on the macroscopic structure and morphology. The mechanical and tribological properties of these films have been investigated by nanoindentation, nano tribo tests, and nano scratch tests. The hardness of a 4-μm-thick film deposited with 17% methane was about 40 GPa, the indentation modulus 387 GPa, and the elastic recovery 75%. Ball-on-disk tests against an Al₂O₃ ball revealed, after initially higher values, a friction coefficient of ≤0.1. Tribo tests and scratch tests proved a strong adhesion and a protective effect on silicon substrates. Finally, the correlations between the macroscopic structure of the films and their mechanical and tribological properties are discussed.     

Wettability and protein adsorption on ultrananocrystalline diamond/amorphous carbon composite films

Ultrananocrystalline diamond/amorphous carbon (UNCD/a-C) composite films have been prepared by microwave plasma chemical vapour deposition (MWCVD) from 17% CH₄/N₂ mixtures and modified with O₂ and CHF₃ plasmas, which changed the surface termination from hydrogen to oxygen and fluorine, respectively. X-ray photoelectron spectroscopy (XPS) showed that successful oxidation and fluorination of the UNCD surface has been achieved with surface O or F concentrations of ca. 12 at.%. None of the plasma modification processes led to a change of the film topography as studied by atomic force microscopy (AFM); for all samples the rms roughness was in the range of 10–12 nm. The UNCD/a-C films with different terminations were characterized by contact angle measurements with water, formamide and benzyl alcohol; from the results obtained the surface energy was calculated. The adsorption of albumin and fibrinogen to the different UNCD/a-C samples was assessed by an inverted enzyme-linked immunosorbent assay (ELISA). The determined albumin/fibrinogen ratios, which could be used to evaluate the tendency of thrombus formation, are correlated with the surface properties of as-deposited and modified UNCD/a-C films.     

Investigation of the nucleation and growth mechanisms of nanocrystalline diamond/amorphous carbon nanocomposite films

Nucleation and growth, but especially the development of the morphology of nanocrystalline diamond/amorphous carbon (NCD/a-C) nanocomposite films have been investigated by systematic variation of three important parameters, namely the deposition time, the growth rate, and the substrate pre-treatment used to enhance the nucleation density. The films have been characterized, among others, by scanning electron microscopy, atomic force microscopy, and Fourier transform infrared spectroscopy. It is shown that, by successive addition of ultradispersive diamond powder to the suspension of nanocrystalline diamond powder in n-pentane used for the ultrasonic pre-treatment, the nucleation density can be enhanced by two orders of magnitude from 1 · 10⁸ cm^− 2 to > 1 · 10¹⁰ cm^− 2. This reduces the thickness required to achieve closed films from 1 µm to 100 nm. However, once coalescence of the individual nodules emerging from the nucleation sites has taken place the films loose “memory” of the nucleation step and start to develop the typical NCD morphology consisting of larger features with diameters of some hundreds of nm which are in turn composed of much smaller features. Irrespective of the feature size and of the parameters used, the films of this investigation possess AFM rms roughnesses of 9–13 nm, indicating that rms values are not sufficient to characterize NCD surfaces.     

Plasma amination of ultrananocrystalline diamond/amorphous carbon composite films for the attachment of biomolecules

Ultrananocrystalline diamond/amorphous carbon nanocomposite films (UNCD/a-C) have been deposited by microwave plasma chemical vapour deposition at 600 °C from 17% CH₄/N₂ mixtures. The as-grown films turned out to be hydrogen terminated and very stable. Photochemical amination of H-terminated diamond is a well-established route to attach functional groups to such surfaces for applications in biosensors. Here we report on experiments to aminate UNCD surfaces directly by exposure to ammonia plasmas. Thereafter the surfaces were reacted with the heterobifunctional crosslinker molecule SSMCC bearing a N-hydroxysuccinimide (NHS) ester group which should react with the surface NH₂ groups. By means of X-ray photoelectron spectroscopy (XPS), contact angle measurements and fluorescence microscopy it is shown that both steps, plasma amination and SSMCC attachment lead to the desired aims. On the other hand, experiments to attach a thiol-bearing fluorescein molecule directly to H-terminated UNCD films turned out to be partially successful although according to literature such a reaction should be very unlikely.     

Optical properties of ultrananocrystalline diamond/amorphous carbon composite films prepared by pulsed laser deposition

Ultrananocrystalline diamond (UNCD)/amorphous carbon (a-C) composite thin films were grown in ambient hydrogen by pulsed laser deposition using a graphite target, and their optical properties were determined by optical absorption spectroscopy and Raman scattering spectroscopy. Three optical bandgaps exist. Two bandgaps are indirect and their values were estimated to be 1.0 eV and 5.4 eV; these bandgaps correspond to the a-C surrounding the UNCDs and the UNCDs respectively. The third bandgap is direct and has a value of 2.2 eV, which significantly contributes to a large absorption coefficient, (10⁶ cm^− 1 at 3.0 eV). Possible origins of the third bandgaps are the grain boundaries (GBs) between the UNCDs and the a-C since they are specific to the UNCD/a-C composite films. The infrared absorption spectrum and the Raman scattering spectrum revealed the incorporation of hydrogen in the GBs. The hydrogen incorporated in the GBs might also have some influence on the appearance of the direct bandgap and its value.     

Electrical properties of ultrananocrystalline diamond/amorphous carbon nanocomposite films

The electrical surface properties of ultrananocrystalline diamond/amorphous carbon composite films have been investigated by four-point probe I/V and Hall measurements, whereas impedance spectroscopy has been used to establish the electrical bulk properties of the films. It turned out that the surface is p-type conductive with a resistivity of 0.14 Ω cm and a sheet carrier concentration of 7.6 × 10¹³ cm^?2. The bulk resistivity is higher by almost seven orders of magnitude (1.3 × 10⁶ Ω cm). The bulk conduction is thermally activated with an apparent activation energy of 0.17 eV. From Cole–Cole plots of the impedance spectra it can be concluded that there are three different contributions to the bulk conductivity. In order to try to identify these three components contributing to the electrical bulk conduction, Raman spectra have been recorded at five different wavelengths from the IR to UV region. These measurements showed that the UNCD/a-C films consist of at least three components: diamond nanocrystallites, an amorphous carbon matrix, and trans-polyacetylene-like structures probably at the interface between these two.     

X-ray photoemission spectroscopic study of ultrananocrystalline diamond/hydrogenated amorphous carbon composite films prepared by pulsed laser deposition

Chemical bonding configurations of ultrananocrystalline diamond (UNCD)/hydrogenated amorphous carbon (a-C:H) composite films prepared by pulsed laser ablation of graphite were investigated by X-ray photoemission spectroscopy using synchrotron radiation. The spectra were decomposed using a Voigt function after the backgrounds were subtracted by Shirley's method. A narrow full-width half-maximum of the sp³ peak is specific, which might be attributed to existence of a large number of UNCD crystallites in the film. The width was immediately broadened by an argon ion bombardment. Its value became equivalent to that of the a-C:H film after the ion bombardment in the same manner. This implies that UNCD crystallites were easily damaged and destroyed by the ion bombardment.     

Wettability of nanocrystalline diamond films

The wettability of nanocrystalline CVD diamond films grown in a microwave plasma using Ar/CH₄/H₂ mixtures with tin melt (250–850 °C) and water was studied by the sessile-drop method. The films showed the highest contact angles θ of 168 ± 3° for tin among all carbon materials. The surface hydrogenation and oxidation allow tailoring of the θ value for water from 106 ± 3° (comparable to polymers) to 5° in a much wider range compared to microcrystalline diamond films. Doping with nitrogen by adding N₂ in plasma strongly affects the wetting presumably due to an increase of sp²-carbon fraction in the films and formation of C–N radicals.     

Fourier transform infrared spectroscopic study of nitrogen-doped ultrananocrystalline diamond/hydrogenated amorphous carbon composite films prepared by pulsed laser deposition

Nitrogen-doped ultrananocrystalline diamond (UNCD)/hydrogenated amorphous carbon (a-C:H) composite films, which possess n-type conduction with enhanced electrical conductivities, were prepared by pulsed laser deposition and they were structurally studied by Fourier transform infrared (FTIR) spectroscopy. The film with a nitrogen content of 7.9 at.% possessed n-type condition with an electrical conductivity of 18 S/cm at 300 K. The FTIR spectra revealed peaks due to nitrogen impurities, C = N, C-N, and CH_n (n = 1, 2, 3) bands. The sp²-CH_n/(sp²-CH_n + sp³-CH_n), estimated from the area-integration of decomposed peaks, were 24.5 and 19.4% for undoped and 7.9 at.% doped films, respectively. The nitrogen-doping not only form the chemical bonds between carbon and nitrogen atoms such as C = N and C-N bonds but also facilitate the formation of both sp² and sp³ bonds, in particular, the sp³-CH_n bond is preferentially formed. From the analysis of the FTIR spectra, it was found that the hydrogen content in the film is increased with an increase in the nitrogen content. The increased hydrogen content might be owing to the enhanced volume of grain boundaries (GBs) between UNCD grains, and those between UNCD grains and an a-C:H matrix, which is caused by a reduction in the UNCD grain size. The CH_n peaks predominantly come from an a-C:H matrix and GBs. Since the nitrogen-doping for a-C:H has been known to be hardly effective, the n-type conduction with the enhanced electrical conductivities might be attributed to the sp²-CH_n formation at the GBs.     

Field emission from metal-containing amorphous carbon composite films

Metal-containing (Co, Al and Ti) amorphous carbon composite films (a-C:Me) have been prepared by the filtered cathodic arc technique using metal-containing graphite targets at room temperature. Field emission properties of the heat-treated a-C:Me films were improved and were found to be dependent on the metal content and variety of metals. After heat-treatment at 550°C in a mixture of acetylene and nitrogen gases, the field emission properties of a-C:Co films were significantly improved, in which Co acted as catalysts to enhance graphitization as well as formation of carbon nanotubes during heat-treatment. A threshold electric field of less than 2 V/μm was obtained from the heat-treated a-C:Co composite films without conditioning. The heat-treated a-C:Al and a-C:Ti films, though the conditioning step could be avoided and relatively low threshold fields could be obtained, exhibited relatively low emission site densities, however. The a-C:Me films, which can be deposited with a high rate at room temperature and require a relatively low temperature, heat-treatment process to enhance electron emission, are promising for practical applications in field emission display.     

Carbon nanotubes grown on cobalt-containing amorphous carbon composite films

Carbon nanotubes (CNTs) have been produced on silicon wafer by filtered cathodic vacuum arc technique using cobalt-containing graphite targets followed by thermal chemical vapor deposition. The Co-containing amorphous carbon (a-C:Co) composite films have various contents of Co as a catalyst for CNTs growth. It is found that dense and random CNTs were grown on the a-C:Co composite film deposited using a 2 at.% Co-containing graphite target and nanoforest CNTs on the composite films using 5, 10 and 15 at.% Co-containing targets. The nanoforest CNTs using a 15 at.% Co-containing target have very good field emission properties with a low threshold field of 1.6 V/μm and a high and stable current density of 2.1 mA/cm² at 3 V/μm, which may result from the smaller diameter of CNTs. It is found that the field emission properties of the CNTs are significantly affected by the diameter of CNTs rather than its orientation.     

Optical emission spectroscopy of deposition process of ultrananocrystalline diamond/hydrogenated amorphous carbon composite films by using a coaxial arc plasma gun

Deposition processes of ultrananocrystalline diamond/hydrogenated amorphous carbon composite (UNCD/a-C:H) films in a hydrogen atmosphere using a coaxial arc plasma gun were spectroscopically investigated with an intensified charge-coupled device (ICCD) camera equipped with narrow-bandpass filters. Strong emissions lasted for more than 100 μs. From the emission time and deposition rate, a supersaturated condition should be strongly realized. This might contribute to the formation of UNCD crystallites. A UNCD crystallite size was estimated to be 2.3 nm from an X-ray diffraction peak. The extremely small value implies that nuclei are repeatedly generated without the subsequent growth. A probable reason is as follows: since the number of carbon species caused using the arc plasma gun is so large as compared to that of hydrogen atoms, which generate from ambient hydrogen molecules by the collision with carbon species, the hydrogen atoms do not effectively contribute to the UNCD crystallite formation. This consideration does not contradict the fact that a coaxial arc plasma gun makes possible UNCD crystallite formation even in vacuum.     

Examination of nanocrystalline TiC/amorphous C deposited thin films

The relationship between structural, chemical and mechanical properties of nanocrystalline TiC/amorphous C (TiC/a:C) thin films was studied. Thin films were deposited by DC magnetron sputtering on oxidized silicon (Si/SiO₂) substrates in argon at 25 °C and 0.25 Pa. The input power of the carbon target was kept at constant value of 150 W while the input power of the titanium target was varied between 15 and 50 W.It was found that all thin films consist of a few nanosized columnar TiC crystallites embedded in carbon matrix. The average size of TiC crystallites and the thickness of the carbon matrix have been found to correlate with Ti content in the films. The mechanical properties of the films have been strictly dependent on their structure. The highest values of the nanohardness (∼66 GPa) and Young's modulus (∼401 GPa) were observed for the film with the highest TiC content which was prepared at the largest input power of Ti target.     

AC behavior of intrinsic nanocrystalline diamond films

Nanocrystalline diamond was prepared by hot filament assisted chemical vapor deposition technique. The nanometer sized dimension of diamond grains was determined by X-ray line broadening. AC electrical response of deposits, constituted by well formed diamond grains, was studied by admittance spectroscopy at different temperatures. Grain boundary and grain surface were considered different regions able to influence differently the frequency dependent AC response. Observed variations in admittance spectra were attributed to a modification of the grain surface response as frequency and temperature rise. A semiconductor to metal-like transition was evidenced in admittance spectra increasing the frequency of applied signal at lower temperatures.     

Gas sensing properties of nanocrystalline diamond films

Toxic gas sensing device with metal electrodes built into nanocrystalline diamond (NCD) is investigated. The NCD morphology is controlled via seeding and/or deposition time. The surface properties and morphology of NCD are studied using scanning electron microscopy (SEM) and atomic force microscopy (AFM). AFM measurements reveal increase in NCD surface area by up to 13%. Gas sensing properties of H-terminated NCD device show high sensitivity towards oxidizing species where the surface conductivity is increased by an order of magnitude for humid air and by three orders of magnitude for COCl₂. The surface conductivity exhibits a small decrease to reducing spices (CO₂, NH₃).     

Thermal analysis of submicron nanocrystalline diamond films

The thermal properties of sub-μm nanocrystalline diamond films in the range of 0.37–1.1 μm grown by hot filament CVD, initiated by bias enhanced nucleation on a nm-thin Si-nucleation layer on various substrates, have been characterized by scanning thermal microscopy. After coalescence, the films have been outgrown with a columnar grain structure. The results indicate that even in the sub-μm range, the average thermal conductivity of these NCD films approaches 400 W m^− 1 K^− 1. By patterning the films into membranes and step-like mesas, the lateral component and the vertical component of the thermal conductivity, k_lateral and k_vertical, have been isolated showing an anisotropy between vertical conduction along the columns, with k_vertical ≈ 1000 W m^− 1 K^− 1, and a weaker lateral conduction across the columns, with k_lateral ≈ 300 W m^− 1 K^− 1.     

Subgap photoluminescence spectroscopy of nanocrystalline diamond films

We report on the effect of ambient conditions and UV irradiation on the subgap photoluminescence of nanocrystalline diamond prepared by microwave plasma enhanced chemical vapour deposition. We measured the photoluminescence of self-supporting membranes of thickness about 290 nm with the grain size up to 40 nm under variable ambient conditions – pressure, temperature, air, nitrogen and helium atmospheres. We have found that intensity of photoluminescence of samples kept under low pressure increases during the time. The photoluminescence intensity of samples under low pressure depends on sample temperature with maximum at about 260 K. The photoluminescence increase can be enhanced substantially by UV irradiation (325 nm) of the sample under certain conditions: temperature greater than ~ 280 K, low pressure of ambient atmosphere. We interpret the experimental results in terms of desorption of water molecules and their interaction with the of individual diamond nanocrystals in the membrane.     

A composite material made of carbon nanotubes partially embedded in a nanocrystalline diamond film

A composite material, made of carbon nanotubes (CNTs) partially embedded in a nanocrystalline diamond film was produced. The diamond film was first decorated with palladium or nickel nanoparticles. An array of nanopores was drilled in the film in a hot filament CVD (HFCVD) reactor thanks to the anisotropic etching that takes place under the nanoparticles. During this etching process, the metallic particles penetrate the diamond film to a controlled depth, thus remaining at the bottom of the nanopores. The buried nanoparticles remain catalytically active and are used to grow a multiwall carbon nanotube forest using HFCVD in the same reactor without breaking the vacuum. The quality of the CNTs was assessed by scanning electron microscopy and Raman spectroscopy. The interface between the carbon nanotubes and the diamond was characterized by ultrasonication, lateral force microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. As a result of these characterizations, we demonstrate that the buried carbon nanotubes exhibit higher mechanical stability and improved electrical behavior compared to CNTs directly grown on the diamond surface.